Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/24—Macromolecular compounds
  • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
  • C04B24/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers containing polyether side chains
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/24—Macromolecular compounds
  • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B24/2641—Polyacrylates; Polymethacrylates
  • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3788—Graft polymers

Definitions

• the present invention relates to graft polymers in which monoethylenically unsaturated monomers including a major proportion of (meth)acrylic acid are grafted on polyethers including a major proportion of ethylene oxide, and also the invention relates to a production process of the graft polymers.
• Graft polymerization of (meth)acrylic acid upon polyether compounds has so far been attempted in various fields of utilization such as polyurethane.
• Japanese Official Patent Provisional Publication No. Showa 55-71710 discloses graft polymers and their production process wherein graft polymerization of 3 to 15 wt. % (based on the total charged amount) of acrylic acid upon polyoxyalkylene compounds is carried out.
• the graft polymers obtained are used as builders, they do not display satisfactory performance, or a very large amount of these polymers need to be added for displaying their performance, because the content of carboxylic acids in these polymers is too low.
• Japanese Official Patent Provisional Publication No. Showa 59-62614 discloses graft polymers and their production process wherein graft polymerization of at least 20 wt. % (based on the graft polymers) of ethylenically unsaturated hydrophilic monomers upon polyglycol ethers having at least one hydrophobic group is carried out.
• a solvent such as water and toluene is used, or even if no solvent is used, the reaction temperature is 90°C or lower. Therefore, the graft efficiency of polymers obtained is low and a large amount of polymers having no grafted part are formed.
• Japanese Official Patent Provisional Publication No. Heisei 3-177406 also discloses the same graft polymers as mentioned above, which are obtained by carrying out polymerization in a water solvent.
• the graft efficiency is low and most of the polymers obtained are polycarboxylic acids having no grafted part. Therefore, in the case of using these polymers as builders, there are the same problems as the above-mentioned prior arts.
• graft polymers cannot be produced which have a high carboxylic acid density and a high graft efficiency and also contain only a small amount of polymers having no grafted part.
• graft polymers obtained by the prior arts are used as builders, sufficient effects are not obtained.
• the process of the present invention for producing a water-soluble graft polymer includes the steps of: preparing:
• the polyether compound (A) used in the present invention includes 80 mol % or more of ethylene oxide as a constituent unit and has a number-average molecular weight of 200 or more, and this compound (A) is, for example, obtained by polymerizing ethylene oxide and other alkylene oxides by conventional methods using water or alcohol as an initiator.
• the alcohols used for obtaining the polyether are, for example, primary alcohols with 1 to 22 carbon atoms such as methanol, ethanol, n-propanol and n-butanol; secondary alcohols with 3 to 18 carbon atoms; tertiary alcohols such as tert-butanol; diols such as ethylene glycol, diethylene glycol, propanediol, butanediol and propylene glycol; triols such as glycerol and trimethylolpropane; polyols such as sorbitol.
• the other alkylene oxides copolymerizable with ethylene oxide are not especially limited. However, propylene oxide and butylene oxide are preferable.
• the content of the other alkylene oxides in the polyether compound (A) needs to be less than 20 mol %. If this content is 20 mol % or more, the graft ratio of a polymer obtained is lowered.
• the polyether compound (A) may be such as produced by esterifying a hydroxyl group of all or part of the terminals of the above-obtained polyether with fatty acids having 2 to 22 carbon atoms or with dicarboxylic acids such as succinic acid, succinic anhydride and adipic acid.
• the number-average molecular weight of these polyethers is 200 or higher, preferably 500 or higher, more preferably 1,000 or higher.
• an upper limit of the molecular weight is 20,000 or lower.
• the upper limit is preferably 6,000 or lower. If the molecular weight of the polyethers is lower than 200, the amount of ungrafted polyethers increases. In such a case, if polymers obtained are used as builders, there occur problems such that the demanded amount of builders increases and therefore satisfactory performance is not obtained.
• the above-mentioned polyether compound (A) it is necessary to subject the above-mentioned polyether compound (A) to graft polymerization with a monomer component (B) including: (b1) 40 to 100 mol % of (meth)acrylic acid and (b2) 0 to 60 mol % of another copolymerizable monoethylenically unsaturated monomer.
• a monomer component (B) including: (b1) 40 to 100 mol % of (meth)acrylic acid and (b2) 0 to 60 mol % of another copolymerizable monoethylenically unsaturated monomer.
• the monomer component (B) is grafted in a ratio of 25 wt. % per 100 wt. % of the polyether compound (A) or more.
• acrylic acid as the component (b1) of the monomer component (B) is grafted in a ratio of 20 wt.
• the ratio of the grafted monomer component (B) is less than 25 wt. %, the carboxylic acid density of graft polymers obtained is lowered and, because of this, there is not obtained satisfactory performance with regard to dispersibility and polyvalent metal ion-chelatability.
• the other monoethylenically unsaturated monomers (b2) copolymerizable with (meth)acrylic acid (b1) are, for example, maleic acid; fumaric acid; maleic anhydride; alkylesters of maleic acid such as dimethyl maleate and diethyl maleate; alkylesters of fumaric acid such as dimethyl fumarate and diethyl fumarate; alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate and stearyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; alkenyl esters of acetic acid such as vinyl acetate; aromatic vinyl such as styrene; (meth)acrylonitrile, (meth)acrolein, (meth)acrylamide; dialkylaminoethy
• maleic acid fumaric acid and maleic anhydride from viewpoints of enhancing a carboxylic acid density of graft polymers to improve their dispersibility and polyvalent metal ion-chelatability.
• the (b1) is within the range of 40 to 100 mol % and the (b2) is within the range of 0 to 60 mol %.
• a preferable copolymerization ratio is as follows: 80 to 100 mol % for the (b1) and 0 to 20 mol % for the monomer (b2).
• the copolymerization ratio of (meth)acrylic acid is less than 80 mol %, the carboxylic acid density of graft polymers obtained is low and, because of this, there is not obtained satisfactory builder performance such as dispersibility and polyvalent metal ion-chelatability.
• the monomer (b2) is a carboxyl group-containing monomer such as maleic acid, fumaric acid and maleic anhydride
• the carboxylic acid density of graft polymers obtained may not be lowered, but there are problems such as a decreased ratio at which maleic acid, fumaric acid and maleic anhydride are introduced into a graft polymer and increase in the amount of residual monomers.
• the graft polymerization is carried out in the presence of a polymerization initiator using substantially no solvent.
• polymerization initiator there can be used conventional radical initiators.
• organic peroxides are especially preferable.
• the organic peroxides are, for example, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; hydroperoxides such as tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide and 1,1,3,3-tetramethylbutyl hydroperoxide; dialkyl peroxides such as di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, ⁇ , ⁇ '-bis(tert-butylperoxy)-p-diisopropylbenzene and ⁇ , ⁇ '-bis(tert-butylperoxy)-p-diisopropylhexyne; peroxy esters such as tert
• the amount of the polymerization initiator is not especially limited. However, the polymerization initiator is preferably used in an amount of 0.1 to 15 wt. %, more preferably 0.5 to 10 wt. %, based on the monoethylenically unsaturated monomers. If the amount used of the initiator is more or less than this range, an efficiency of the monomers grafted upon the polyether is lowered. In addition, the polymerization initiator may be added to the polyether either beforehand separately from or together with the monoethylenically unsaturated monomers.
• the graft polymerization is carried out using substantially no solvent. If water or an organic solvent such as alcohol and toluene is used, the efficiency of the monomers grafted upon the polyether is lowered. In the case where a solvent is used for adding the initiator and the monomers, it is preferable that the amount used of this solvent is as small as possible, more preferably 5 wt. % or smaller based on the amount used of all materials, or that the solvent is removed from a reaction system by evaporation immediately after its adding.
• the polymerization temperature is 100 °C or higher, preferably within the range of 110 to 160 °C . If this temperature is lower than 100°C , the efficiency of the monomers grafted upon the polyether is lowered. In addition, at a temperature higher than 160°C, there may occur thermal decomposition of the polyethers and graft polymers.
• the monomer (b2) in the case where maleic acid, fumaric acid or maleic anhydride is used as the monomer (b2), it is preferable that half or more of the amount used of the monomer (b2) is initially charged together with the polyether compound (A).
• the initiator and a balance of the monomers are separately added dropwise after heating the polyether up to 100 °C or higher.
• a balance of the polyether compound (A) may be mixed with the initiator or monomers and added dropwise.
• the content of polymers of only ungrafted monomer components (B) can be lowered and a water-soluble graft polymer having high purity can be obtained which has not yet been achieved by known arts.
• a water-soluble graft polymer can be obtained in which the content of polymers of only monomer components (B) ungrafted upon the polyether (A) is smaller than 30 wt. %, more preferably smaller than 25 wt. %, per 100 wt. % of all the monomer components (B) used.
• the graft polymer obtained can be used as a dispersant, a scale-inhibiting agent or a detergent builder either by dissolving intactly this polymer in a solvent such as water and alcohol, or by adding a base to this polymer to convert it into its salt.
• a salt are monovalent metal salts such as sodium salts and potassium salts; divalent metal salts such as calcium salts; trivalent metal salts such as aluminum salts; organic amine salts such as ammonium salts, monoethanolamine and triethanolamine.
• water is preferred as a solvent.
• the water-soluble graft polymer obtainable by the production process of the present invention displays good performance as dispersants for inorganic or organic substances which are sparingly soluble in water.
• this polymer displays good performance as dispersants for: heavy or light calcium carbonate used for paper coating; inorganic pigments such as clay; and water slurries of cement, coal and the like.
• this polymer can be used as water-treating agents for inhibiting formation of scale in systems such as cooling water systems, boiler water systems, desalination plants, pulp digestors and black liquor evaporators, and also as fiber-treating agents such as dyeing promoters and electrification-preventing promoters for fibers.
• the water-soluble graft polymer obtainable by the production process of the present invention can be used as a water-absorbent resin by crosslinking this polymer using a crosslinking agent.
• the soluble content of this water-absorbent resin is low, because the above-mentioned graft polymer has a high graft ratio.
• the above-mentioned water-absorbent resin has high salt-resistance, because it contains the polyether in its principal chain.
• the crosslinking is carried out by conventional methods and not especially limited. However, the crosslinking is preferably carried out by a reaction between the crosslinking agent and a carboxyl group of the graft polymer.
• a detergent composition of the present invention contains a surfactant and a builder including the water-soluble graft polymer of the present invention and may be used in any form of powder, solid and liquid.
• the water-soluble graft polymer of the present invention displays good solubility into liquid detergents to which conventional high-molecular builder polyacrylic acid salts or acrylic acid/maleic acid copolymers cannot be added because of their poor compatibility with the liquid detergents.
• the graft polymer of the present invention is preferable as a builder for liquid detergents.
• the surfactant there may be used at least one selected from the group consisting of anionic, nonionic, ampholytic, and cationic surfactants.
• the surfactant and the builder are, for example, used in a ratio of 0.5 to 200 parts by weight of the builder per 100 parts by weight of the surfactant. However, the ratio between them is not limited to this range. If the amount of the builder is larger than the above range, there are economical disadvantages. If the amount of the builder is smaller than the above range, there cannot practically be expected merits which are obtained by adding the builder.
• the builder of the present invention may be used in combinations with conventional builders such as zeorite, citric acid salts, polyacrylic acid salts, acrylic acid/maleic acid copolymer salts, condensed phosphoric acid salts and silicic acid salts.
• the ratio used of the builder of the present invention may properly be determined and is not especially limited.
• detergent composition of the present invention there may be added other components, as usually used for conventional detergent compositions, such as alkalis, inorganic electrolytes, chelating agents, re-pollution preventing agents, enzymes, bleachers, fluorescent agents, antioxidizing agents, solubilizers, coloring agents and perfumes.
• other components such as alkalis, inorganic electrolytes, chelating agents, re-pollution preventing agents, enzymes, bleachers, fluorescent agents, antioxidizing agents, solubilizers, coloring agents and perfumes.
• a 10 % aqueous sodium hydroxide solution was added in such an amount that acrylic acid, added dropwise, was completely neutralized, and then the solution was heated while stirring at reflux temperature for 1 hour to obtain an aqueous solution of a sodium salt of a graft polymer 1.
• a 10 % aqueous sodium hydroxide solution was added in such an amount that acrylic acid, added dropwise, was completely neutralized, and then the solution was heated while stirring at reflux temperature for 1 hour to obtain an aqueous solution of a sodium salt of a graft polymer 2.
• a 10 % aqueous sodium hydroxide solution was added in such an amount that acrylic acid, added dropwise, was completely neutralized, and then the solution was heated while stirring at reflux temperature for 1 hour to obtain an aqueous solution of a sodium salt of a graft polymer 3.
• a 10 % aqueous sodium hydroxide solution was added in such an amount that methacrylic acid, added dropwise, was completely neutralized, and then the solution was heated while stirring at reflux temperature for 1 hour to obtain an aqueous solution of a sodium salt of a graft polymer 4.
• a 10 % aqueous sodium hydroxide solution was added in such an amount that acrylic acid, added dropwise, was completely neutralized, and then the solution was heated while stirring at reflux temperature for 1 hour to obtain an aqueous solution of a sodium salt of a graft polymer 8.
• a 10 % aqueous sodium hydroxide solution was added in such an amount that 90 % of acrylic acid was neutralized, and then the solution was stirred at room temperature to obtain an aqueous solution of a sodium salt of a graft polymer 9.
• a 10 % aqueous sodium hydroxide solution was added in such an amount that acrylic acid, added dropwise, was completely neutralized, and then the solution was heated while stirring at reflux temperature for 1 hour to obtain an aqueous solution of a sodium salt of a graft polymer 10.
• a 10 % aqueous sodium hydroxide solution was added in such an amount that acrylic acid, added dropwise, was completely neutralized, and then the solution was heated while stirring at reflux temperature for 1 hour to obtain an aqueous solution of a sodium salt of a comparative polymer 5.
• the graft ratios of the polymers obtained in Examples and Comparative Examples were determined by examining solubility of acid type polymers in benzene (usually, polycarboxylic acids such as polyacrylic acids and acrylic acid/maleic acid copolymers do not dissolve in solvents such as benzene, toluene and chloroform).
• polymers were prepared as follows.
• the graft polymer 1 of Example 1 and the comparative polymers 1 and 4 of Comparative Examples 1 and 4 were evaluated as dispersing agents as follows.
• a slurry was prepared so that a ratio by weight of light calcium carbonate (trade name: Brilliant #1500, made by Shiraishi Kogyo Kaisha, Ltd.) to water might be 60/40.
• a ratio by weight of light calcium carbonate (trade name: Brilliant #1500, made by Shiraishi Kogyo Kaisha, Ltd.) to water might be 60/40.
• To this slurry was added each of the graft polymer and comparative polymers while stirring to adjust the viscosity of the slurry.
• the resulting viscosity of the slurry was measured using a B type rotation viscometer to show the viscosity in the unit "cps".
• the slurry had almost no fluidity and therefore the viscosity measurement was impossible. Results were shown in Table 2.
• the graft polymer of Example 1 displayed good performance as a dispersing agent and also lowered the viscosity of the calcium carbonate slurry even by adding a small amount of the graft polymer.
• Sodium salts of the graft polymers 1, 3, 5 to 14, 19 and 20 of Examples 1, 3, 5 to 14, 19 and 20 as well as a sodium salt of the comparative polymer 4 of Comparative Example 4 were used as sample builders to prepare detergent compositions with the following formulation: 20 wt. % of sodium alkylbenzenesulfonate, 20 wt. % of the sample builder, 10 wt. % of #2 sodium silicate, 10 wt. % of anhydrous sodium carbonate and 40 wt. % of anhydrous sodium sulfate.
• Washing ratio (%) (R W - R S )(R O - R S ) ⁇ 100 where: R O is surface reflectivity of an original white cloth of the artificially polluted cloth; R S is surface reflectivity of the artificially polluted cloth before washing; and R W is surface reflectivity of the artificially polluted cloth after washing.
• the detergent composition containing no builder was prepared by combining water instead of the sample builder as combined above. Results were shown in Table 6. When compared with the polymer of Comparative Example, the graft polymers of Examples displayed good buildability.

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• 1994
  • 1994-08-05 EP EP94305849A patent/EP0639592A1/de not_active Withdrawn

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